Waterborne exposure to PFOS causes disruption of the hypothalamus-pituitary-thyroid axis in zebrafish larvae

Thyroid hormones (THs) play an important role in the normal development and physiological functions in fish. Environmental chemicals may adversely affect thyroid function by disturbing gene transcription. Perfluorooctane sulfonate (PFOS), a persistent compound, is widely distributed in the aquatic environment and wildlife. In the present study, we investigated whether PFOS could disrupt the hypothalamic– pituitary–thyroid (HPT) axis. Zebrafish embryos were exposed to various concentrations of PFOS (0, 100, 200 and 400 lg L 1) and gene expression patterns were examined 15 d post-fertilization. The expression of several genes in the HPT system, i.e., corticotropin-releasing factor (CRF), thyroid-stimulating hormone (TSH), sodium/iodide symporter (NIS), thyroglobulin (TG), thyroid peroxidase (TPO), transthyretin (TTR), iodothyronine deiodinases (Dio1 and Dio2) and thyroid receptor (TRa and TRb), was quantitatively measured using real-time PCR. The gene expression levels of CRF and TSH were significantly up-regulated and down-regulated, respectively, upon exposure to 200 and 400 lg L 1 PFOS. A significant increase in NIS and Dio1 gene expression was observed at 200 lg L 1 PFOS exposure, while TG gene expression was down-regulated at 200 and 400 lg L 1 PFOS exposure. TTR gene expression was down-regulated in a concentration-dependent manner. Up-regulation and down-regulation of TRa and TRb gene expression, respectively, was observed upon exposure to PFOS. The whole body thyroxine (T4) content remained unchanged, whereas triiodothyronine (T3) levels were significantly increased, which could directly reflect disrupted thyroid hormone status after PFOS exposure. The overall results indicated that PFOS exposure could alter gene expression in the HPT axis and that mechanisms of disruption of thyroid status by PFOS could occur at several steps in the synthesis, regulation, and action of thyroid hormones.

自交联材料在肥料养分控释上的应用研究

目前在包膜控释肥料方面的研究热点是采用树脂型包膜材料制备包膜肥料，并且取得了一定的成绩，控释效果比较良好，但由于树脂材料需用大量有机溶剂，给生产成本和工艺都带来了新的问题。本试验针对此问题，选用水性聚氨酯（PU）和水性丙烯酸（PA）作为包膜材料，应用旋转包膜工艺和流化床包膜工艺制备包膜肥料，采用水培法、淋溶法、土培法、电镜观察等方法对其进行释放性能评价，最终确定水性聚氨酯和水性丙烯酸在肥料中应用的效果。结果表明： 以旋转包膜工艺、用水性聚氨酯（PU）为膜材料制备的9种包膜肥料，并做了封闭处理，通过扫描电镜观察都形成了致密连续的控释膜，经评价都具有一定的控释效果，其中CRF-6（水性聚氨酯用量6%，封闭剂用量3%）、CRF-9（水性聚氨酯用量9%，封闭剂用量3%）两种包膜肥料控释性能较优，水培条件下其氮素初期溶出率分别为29.11%和19.48%，钾素初期溶出率分别为33.15%和24.93%。各种评价方法结果表明：同一材料不同包膜量控释效果比较：6%用量优于9%用量，优于3%用量。封闭剂用量在2%时效果相对较好。 以流化床包膜工艺、用水性聚氨酯（PU）和水性丙烯酸（PA）为膜材料制备的15种包膜肥料，经检测FCRF-9（PA:PU=1:2，9%）、FCRF-11（PA:PU=1:1，6%）和FCRF-12（PA:PU=1:1，9%）这3种肥料控释效果最为突出，在水培条件下其氮素初期溶出率分别为12.58%、15.62%和16.02%。材料组合以水性聚氨酯（PU）和水性丙烯酸（PA）以1：2复合包膜最理想。对于同一包膜材料不同用量控释效果顺序：9%用量优于6%用量，优于3%用量。与普通肥料肥料相比，包膜肥料吸湿率大幅下降。 旋转包膜工艺与流化床包膜工艺比较表明：在低用量时，水性包膜材料在流化床包膜工艺与旋转包膜工艺制备肥料控释性能没有差异；在高用量时，流化床包膜工艺比旋转包膜工艺更适合应用于水性高分子材料肥料包膜。

The main factor influencing the tensile properties of surface nano-crystallized graded materials

The improved mechanical properties of surface nano-crystallized graded materials produced by surface severe plastic deformation ((SPD)-P-2) are generally owing to the effects of the refined structure, work-hardened region and compressive residual stress. However, during the (SPD)-P-2 process, residual stress is produced simultaneously with work-hardened region, the individual contribution of these two factors to the improved mechanical properties remains unclear. Numerical simulations are carried out in order to answer this question. It is found that work hardening predominates in improving the yield strength and the ultimate tensile strength of the surface nano-crystallized graded materials, while the influence of the residual stress mainly emerges at the initial stage of deformation and decreases the apparent elastic modulus of the surface nano-crystallized graded materials, which agrees well with the experimental results. (C) 2010 Elsevier B.V. All rights reserved.

青海湖地区芨芨草草地土壤种子库的初步研究

选择青海湖地区的次生芨芨草草地为研究对象,以围栏内封育和围栏外自由放牧的草地做对照,研究了围栏内外土壤种子库的萌发状况、密度和数量、物种多样性,以及土壤种子库与地上植被的关系。结果表明,围栏内外土壤种子库的萌发趋势非常相似,但是萌发种子累计数量不同;围栏内外土壤种子库中萌发种子的平均密度分别为3660和2460粒·m-2,围栏内萌发种子数比围栏外提高了48.8%;围栏内外土壤种子库的物种多样性指数差异较大,围栏内外丰富度指数R1分别为17和13,R2为3.693和2.832,丰富度围栏内大于围栏外,多样性指数和丰富度指数具有相同的规律,均匀度指数围栏内外分别为0.812和0.857,则是围栏外大于围栏内。围栏内外地上植被群落组成存在显著差异,围栏内的封育草地的物种丰富度和多样性指数均大于围栏外的放牧草地,而均匀度指数则呈相反趋势。

基于半马尔科夫条件随机场的命名体识别及其关系抽取研究

随着互联网和电子化办公的发展，出现了大量的文本资源。信息抽取技术可以帮助人们快速获取大规模文本中的有用信息。命名体识别与关系抽取是信息抽取的两个基本任务。本文在调研当前命名体识别和实体关系抽取中采用的主要方法的基础上，分别给出了解决方案。论文开展的主要工作有：（1）从模型选择和特征选择两个方面总结了命名体识别及实体关系抽取的国内外研究现状，重点介绍用于命名体识别的统计学习方法以及用于实体关系抽取的基于核的方法。（2）针对当前命名体识别中命名体片段边界的确定问题，研究了如何将 Semi-Markov CRFs 模型应用于中文命名体识别。这种模型只要求段间遵循马尔科夫规则，而段内的文本之间则可以被灵活的赋予各种规则。将这种模型用于中文命名体识别任务时，我们可以更有效更自由的设计出各种有利于识别出命名体片段边界的特征。实验表明，加入段相关的特征后，命名体识别的性能提高了 4-5 个百分点。（3）实体关系抽取的任务是判别两个实体之间的语义关系。之前的研究已经表明，待判别关系的两个实体间的语法树结构对于确定二者的关系类别是非常有用的，而相对成熟的基于平面特征的关系抽取方法在充分提取语法树结构特征方面的能力有限，因此，本文研究了基于核的中文实体关系抽取方法。针对中文特点，我们探讨了卷积（Convolution）核中使用不同的语法树对中文实体关系抽取性能的影响，构造了几种基于卷积核的复合核，改进了最短路依赖核。因为核方法开始被用于英文关系抽取时，F1 值也只有40%左右，而我们只使用作用在语法树上的卷积核时，中文关系抽取的F1 值达到了35%，可见核方法对中文关系抽取也是有效的。

新型二维异核配位聚合物{[NdBi(cydta)(NO_3)_2(H_2O)_4]·2.5H_2O}_n的晶体结构与热分解

由Bi(Hcydta).5H2O和Nd(NO3).6H2O按1︰1的物质的量比,在水溶液中合成了含Bi(III)-Nd(III)的异核配位聚合物{[(NO3)Nd(H2O)4(μ3-cydta)Bi(μ-ONO2)].2.5H2O}n.用元素分析、红外光谱、热重-差热和X射线单晶衍射等手段对标题配合物的组成和结构进行了表征.该配合物属三斜晶系,空间群P1,晶胞参数:a=0.9235(3)nm,b=1.0902(4)nm,c=1.4253(5)nm,α=71.840(4)°,β=86.877(4)°,γ=76.991(4)°,Z=2,Mr=936.65,V=1.3284(8)nm3,Dc=2.342g.cm-3,μ=8.646mm-1,F(000)=900,最终偏离因子R1=0.0406,wR2=0.1124.在该配合物中,铋(III)与配体cydta4-的4O2N和1个硝酸根中1个O原子以及邻位分子的硝酸根形成8配位的畸变双帽三棱柱.钕(III)与4个水分子的O,1个硝酸根中2个O以及来自3个不同配体cydta4-的桥联羧基O结合,形成9配位的三帽三棱柱构型.羧酸根在Bi—Nd和硝酸根在Bi—Bi间的桥联作用...

Synthesis and structural characterization of a new molecule-based complex constructed from dodecamolybdophosphoric acid and imidazole

A new compound, (CH5N2)(3)(PMo12O40CH4N23H2O)-C-.-H-. (1), was synthesized and structurally characterized by elemental analyses, IR spectra, UV spectra, NMR spectra and ESR spectra. This is, to our knowledge, the first example of an imidazole-polyoxometalate species. The compound was recrystallized from N,N-dimethylformamide (DMF), and then black block-like crystals of (C3H5N2)(4)((PMoMo11O40)-Mo-V-O-VI)(.)4C(3)H(7)NO(.) 2H(2)O (2), were obtained. It crystallizes in a triclinic space group P (1) over bar with n=12.423(3) Angstrom, b=12.666(3) Angstrom, c=13.341(3) Angstrom, alpha=70.56(3)degrees, beta=71.16(3)degrees, gamma=64.18(3)degrees, V= 1742.3(6) Angstrom(3), Z=1, R1 = 0.0585, wR2 = 0.1885. An X-ray crystallographic study showed that the crystal structure is constructed by electrostatic attractions and hydrogen bonds between a dodecamolybdophosphoric anion and an imidazole. The imidazole and DMF molecules occupy cavities in a polyoxometalate lattice ordered along a c-axis. The structure of (2) is similar to that of (1) from a comparison of both IR spectra and TGA Curves.

Hydrothermal synthesis and crystal structure of a novel compound: [Ni(phen)(3)](2)[(SiMo10V2O40)-O-IV((VO)-O-IV)2]center dot 2H(2)O

A novel compound [Ni(phen)(3)](2)[(SiMo10V1/2O40)-O-V((VO)-O-IV)(2)] . 2H(2)O has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the triclinic, system, space group P-1, a = 12.378(4) Angstrom, b = 14.148(5) Angstrom, c = 14.316(2) Angstrom, alpha = 105.91(2)degrees, beta = 95.31(2)degrees, gamma = 96.89(3)degrees, V = 2373.0(12) Angstrom(3), Z = 1, (lambdaMo(Kalpha)) = 0.71073 Angstrom, R1 (wR2) = 0.0869(0.2174). Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range of 1.51 < theta < 22.50degrees using the omega-scan technique. Empirical absorption correction (psi scan) was applied. The structure was solved by the direct method and refined by the Full-matrix least-squares on F-2 using the SHELXL-97 software. X-ray crystallographic study showed that the title compound contained a bi-capped alpha-Kegin-type [(SiMo10V2O40)-O-IV((VO)-O-IV)(2)](4-) polyoxoanion.

Synthesis, characterization and crystal structures of dibenzo-18-crown-6 sodium isopolytungstates

Two novel dibenzo-18-crown-6 sodium isopolytungstates, [(DB18C6)(CH3OH)Na](2)W(6)O(19)(.)DB18C6(.)H(2)O 1 and [(DB18C6)(DMF)(2)Na](4)W(10)O(32)(.)2DMF(.)2H(2)O 2, have been synthesized in mixed methanol and acetonitrile solvents and characterized by elemental analysis, TGA, IR and single crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic space group C2/c with a = 23.182(8), b = 19.527(2), c = 18.737(3) Angstrom, beta = 115.15(2)degrees, V = 7678(3) Angstrom(3), Z = 4, and R1(wR2) = 0.0611(0.1504). The compound 2 crystallizes in the monoclinic space group P21/n with a = 16.516(2), b = 22.325(6), c = 20.425(7) Angstrom, beta = 91.78(2)degrees, V = 7528(3) Angstrom(3), Z = 2, and R1(wR2) = 0.0397(0.0773). The compound 1 exhibits a novel organic-inorganic sandwich-type structure, in which the crown ether-sodium complexes are coordinated to the terminal oxygen atoms of W6O192-. In compound 2, all Na+ ions are thoroughly enveloped into the organic moieties of crown ether and DMF molecules and are connected with the 'naked' polyanions W10O324- via the electrostatic attraction.

A study of resonance electron capture ionization on a quadrupole tandem mass spectrometer

Procedures that allow the realization of resonance electron capture (REC) mode on a commercial triple-quadrupole mass spectrometer, after some simple modifications, are described, REC mass spectrometry (MS) and tandem mass spectrometry (MS/MS) experiments were performed and spectra for some compounds were recorded. In particular, the charge-remote fragmentation (CRF) spectra of [M - H](-) ions of docosanoic and docosenoic acids under low-energy collisionally activated dissociation (CAD) conditions were obtained, and showed that there were no significant differences for [M - H](-) ions produced at different resonances (i,e. for [M - H](-) ions with different structures). This observation was explained on the basis of results obtained from deuterium-labeled fatty acids, which showed that different CRF ions (but with the same m/z value in the absence of labels) could be produced by different mechanisms, and all of them were obviously realized under CAD conditions that made spectra practically indistinguishable. The other example, which compared the REC-MS/MS spectrum of [M - H](-) ions and EI-MS/MS spectrum of M+. ions of daidzein, demonstrated the potential of the REC-MS/MS technique for more complex structure elucidation. Copyright (C) 2000 John Wiley & Sons, Ltd.

Synthesis and crystal structure of a new supermolecular compound: [C12H24O6][H3PMo12O40]center dot 22H(2)O (C12H24O6=18-crown-6)

The title compound, [C12H24O6][H3PMo12O40]. 22H(2)O, was synthesized by the self-assembly of 18-crown-6 (abbreviated as C12H24O6 or 18C6) and H3PMo12O40 in the mixed solvent of CH3OH and CH3CN, and was characterized by IR, H-1 NMR and Xray diffraction for the first time. Crystal data: Triclinic, P (1) over bar, a = 13.428(3) Angstrom, b = 13.557(3)A, c = 14.642(3) Angstrom, a = 105.39(3)degrees, beta = 90.06(3)degrees, gamma = 119.56(5)degrees, V = 2207.5(8) Angstrom(3), Z = 1, R1 = 0.0719, wR2 = 0.1990. It has a disordered alpha-Keggin PMo12O403- anion, which contains the strong alternating short (mean 1.844 Angstrom) and long (mean 1.958 Angstrom) Mo-O-Mo bonds. In the unit cell, crown ethers and molybdophosphates are alternatively arranged in good order along c-axis. An oxonium ion is located at the center of a crown ether molecule., Oxonium ion interacts with 18C6 by the means of hydrogen bonds (mean 2.7771 Angstrom), which are electrostatic or resonant. The observations show the existence of [H3O(C12H24O6)](+) (C) 2000 Elsevier Science B.V. All rights reserved.

长链烷氧基取代苯基卟啉衍生物的解吸电子离子化质谱

长链烷氧基取代苯基卟啉化合物是一类性能良好的充电膜材料及照相感光材料.本文对合成一系列四-(对-烷氧基笨基)卟啉(取代基如式(1)R1=R2=R3=R4=H;(2)R1=C16H33,R2=R3=R4=H;(3)R1=R2=C16H33,R3=R4=H;(4)R1=R2=R3=C16H33,R4=H;(5)R1=R2=R3=R4=C16H33)进行质谱分进,结果表明,当用DEI电离方式时,不仅能给出较大丰度的分子离子峰,而且其EDIMS谱还清楚地反映出卟啉苯环羟基氢取代基团的丢失规律.然而其他电离方式却难以达到这样的效果.2 样品与仪器 部分所用样品承吉林大学王永祥博士赠送.质谱实验在 VG公司生产的 Quattro三级四极串联质谱仪上进行,采用DCI方式进样,但不通反应气故称DEI,离子源温度为100℃,发射电流260μA,用IBM386数据系统采集数据.

STUDIES ON OLEFIN-COORDINATING TRANSITION-METAL CARBENE COMPLEXES .20. SYNTHESIS OF 1,3-CYCLOHEXADIENE(DICARBONYL) [ETHOXY(ARYL)-CARBENE]IRON COMPLEXES AND THEIR PHOSPHINE ADDUCTS - CRYSTAL-STRUCTURE OF C6H8(CO)2FEC(OC2H5)C6H4CH3-O

Reaction of 1,3-cyclohexadiene(tricarbonyl)iron (1) with ortho-substituted aryllithium reagents ArLi (Ar=o-CH3C6H4, o-CH3OC6H4, o-CF3C6H4) in ether at low temperature, and subsequent alkylation of the acylmetalates formed with Et3OBF4 in aqueous solution at 0-degrees-C or in CH2Cl2 at -60-degrees-C gave the 1,3-cyclohexadiene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes (eta4-C6H8)(CO)2FeC(OC2H5)Ar (3, Ar = o-CH3C6H4; 4, Ar = o-CH3OC6H4), and the isomerized product (eta3-C6H8)(CO)2FeC(OC2H5)C6H4CF3-o (5), respectively, among which the structure of 3 has been established by an X-ray diffraction study. Complex 3 is monoclinic, space group P2(1) with a = 8.118(4), b = 7.367(4), c = 14.002(6) angstrom, beta = 104.09(3)-degrees, V = 812.2(6) angstrom3, Z = 2, D(c) = 1.39 g cm-3, R = 0.056, and R(w) = 0.062 for 976 observed reflections. Complexes 3 and 5 were converted into the chelated allyliron phosphine adducts(eta3-C6H8)(CO)2(PR31)FeC(OC2H5)Ar (6, Ar = o-CH3C6H4, R1 = Ph; 7, Ar = o-CH3C6H4, R1 = OPh; 9, Ar = o-CF3C6H4, R1 = Ph), by reaction with phosphines in petroleum ether at low temperatures.

海洋红藻多管藻和松节藻的化学成分及抗氧化活性研究

海洋生物具有产生丰富多样的次生代谢产物的能力，其中红藻门松节藻科海藻卤代次生代谢产物以其结构新颖、生物活性独特引起了天然产物化学家的重视。 本论文对海洋红藻多管藻和松节藻进行了化学成分研究，综合利用各种色谱学方法 (硅胶柱层析、反相硅胶柱层析、凝胶Sephadex LH-20柱层析、半制备高效液相色谱以及重结晶等) 和现代波谱学技术 (IR、UV、EI-MS、FAB-MS、HR-ESI-MS、CD、1H-NMR、13C-NMR、DEPT、1H-1H COSY、HSQC、HMBC等)，共分离鉴定了100个化合物，发现25个新化合物。 从多管藻中分离鉴定38个化合物 (24个溴酚化合物)，其中7个新化合物 (均为溴酚化合物)，包括1个菲并呋喃结构溴酚 (P1), 2个二氢菲结构溴酚 (P2, P3)，1个含 5,7-dihydrodibenzo[c,e]oxepine 结构溴酚 (P4)和3个简单溴酚 (P5, P6, P7)。P1 (urceolatin) 属首例报道的具有菲并呋喃结构的天然产物，从该种中分离的化合物P12 和 P13 可能是其生源合成的前体。P2和P3为第二例报道的具有二氢菲结构的溴酚化合物。 从松节藻中分离并鉴定了62 个化合物，其中18 个为溴酚类新化合物，44 个为已知化合物。化合物具有多变的取代基团，包括2 个脲基吡咯烷酮溴酚化合物 (R1, R2), 4 个γ-脲基丁酸溴酚化合物 (R3-R6)，5 个酰胺溴酚化合物 (R7, R8, R9, R13, R14)，1 个溴酚砜化合物 (R12), 1 个Xanthene 溴酚化合物 (R10)和5 个简单溴酚化合物 (R11, R15, R16, R17, R18)。R1、R2 是首例报道的含有脲基吡咯烷酮片段的天然产物，R10 为首次报道的溴代Xanthene 类天然产物。 对分离到的化合物进行了清除DPPH 和ABTS两种自由基活性的筛选。结果发现溴酚类天然产物具有显著的DPPH自由基清除活性，其中R3 的IC50 仅为3.3 μM, 其活性强度约为阳性对照BHT (IC50 为82.1 μM) 的24倍。另外，溴酚类天然产物对ABTS自由基有较强的清除活性，R2 的TEAC（Trolox efficency activity capacity）值为5.2 mM，约为阳性对照 (ascorbic acid, 1.02 mM) 的 5 倍。初步的构效关系研究发现，稠环分子、多羟基和邻位甲氧基等结构特点能有效增强DPPH 自由基清除活性；特殊取代基如脲基、吡咯烷酮等含有氮原子的基团，能有效增强ABTS 自由基清除活性，多羟基、溴代等结构特点也使其活性有所增强。 本研究结果丰富了海藻卤代化合物的结构类型，为多管藻和松节藻的合理利用提供了一定的科学依据。

复方治疗慢性肾衰海洋新药的初步研究

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